WO2013072257A1 - Procédé pour l'élimination catalytique de dioxyde de carbone et de nox de d'effluents gazeux - Google Patents

Procédé pour l'élimination catalytique de dioxyde de carbone et de nox de d'effluents gazeux Download PDF

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Publication number
WO2013072257A1
WO2013072257A1 PCT/EP2012/072286 EP2012072286W WO2013072257A1 WO 2013072257 A1 WO2013072257 A1 WO 2013072257A1 EP 2012072286 W EP2012072286 W EP 2012072286W WO 2013072257 A1 WO2013072257 A1 WO 2013072257A1
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Prior art keywords
catalyst
exhaust gases
reactor
water
activated carbon
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PCT/EP2012/072286
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German (de)
English (en)
Inventor
Alain Strickroth
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Cppe Carbon Process & Plant Engineering S.A.
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Publication date
Priority to ES12781361.6T priority Critical patent/ES2666493T3/es
Priority to SG11201401771TA priority patent/SG11201401771TA/en
Application filed by Cppe Carbon Process & Plant Engineering S.A. filed Critical Cppe Carbon Process & Plant Engineering S.A.
Priority to PL12781361T priority patent/PL2782662T3/pl
Priority to CA2852817A priority patent/CA2852817C/fr
Priority to EP12781361.6A priority patent/EP2782662B1/fr
Priority to NO12781361A priority patent/NO2782662T3/no
Priority to BR112014011549A priority patent/BR112014011549A2/pt
Priority to JP2014540482A priority patent/JP6614774B2/ja
Priority to DK12781361.6T priority patent/DK2782662T3/en
Priority to CN201280055983.8A priority patent/CN104254385B/zh
Priority to MX2014005774A priority patent/MX349586B/es
Priority to KR1020147015844A priority patent/KR20140101775A/ko
Priority to EA201400580A priority patent/EA024177B1/ru
Priority to AU2012339000A priority patent/AU2012339000B2/en
Priority to US14/357,498 priority patent/US9375681B2/en
Publication of WO2013072257A1 publication Critical patent/WO2013072257A1/fr
Priority to TNP2014000178A priority patent/TN2014000178A1/en
Priority to MA37089A priority patent/MA35821B1/fr
Priority to ZA2014/04132A priority patent/ZA201404132B/en
Priority to IN4592DEN2014 priority patent/IN2014DN04592A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B01D2255/702—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates generally to a process for the catalytic removal of carbon dioxide and NO x from exhaust gases.
  • An object of the present invention is to provide a method which removes mainly NOx and carbon dioxide from exhaust gases.
  • This object is achieved by a method for the catalytic removal of carbon dioxide and NOx from exhaust gases in a reactor filled with activated carbon catalyst.
  • This process is characterized by the following steps: a) saturation of the catalyst with water,
  • An advantage of the method is that NOx and CO2 are extracted from the gas phase under the form NO3 " and C and present according to the method as a liquid (dissolved in water NO3 " ) or solid and can be used further.
  • the process makes it possible to treat exhaust gases from industrial plants in particular from combustion exhaust gases containing carbon dioxide and ((eg from natural gas combustion) and these two pollutants simultaneously and in parallel, ie in a process entirely or in part from the exhaust gases remove.
  • the catalyst should advantageously be saturated or partially saturated with NOx prior to first use.
  • saturated or partial saturation of the catalyst with NOx is understood in the context of the present invention, that the exhaust gases then reach the activated carbon catalyst, have sufficient exothermic conversion energy, which takes place through the NO x conversions in NO3 " to start with the CO2 conversion afterwards. This corresponds, as emerged from experiments, a magnitude of 0.1 - 0.3 kg NOx / m 3 activated carbon catalyst.
  • saturated of the catalyst with water means that the catalyst is charged with water or steam until water runs out of the reactor, which corresponds to the experiments described below emerged, of the order of 250 to 550 kg of water / m 3 activated carbon catalyst.
  • the process is carried out here with a "wet" catalyst
  • the catalyst is wet before the beginning of the reaction and is sprayed with water before and during the process and the resulting solids are formed During the process, ie without the process having to be stopped, it is washed off, but in CN 101 564 640 the catalyst is run "dry” and only after the cleaning no longer works effectively (step 5 of the process) is the process interrupted and the catalyst is sprayed with water to wash away the adherent products, yielding a dilute liquid acid with residues (step 6 of the process).
  • the reactor in process CN 101 564 640 is added in step 7 at 100 ° C to 120 ° C warm air to dry the catalyst before the reactor is put back into operation.
  • the gases to be treated in the process of CN 101 564 640 also contain water vapor only in a very low concentration (2-12 vol.%).
  • At least 30 vol.% Of the CO2 contained in the exhaust gases is converted, preferably at least 50 vol.%, Especially preferably at least 70% by volume and in particular at least 90% by volume. Furthermore, at least 20% by volume of the NO.sub.x contained can be converted, preferably at least 50% by volume, particularly preferably at least 70% by volume and in particular at least 90% by volume being decomposed
  • NO x is understood as meaning nitrogen oxides, nitrous gases or nitrogen oxides as generic terms for the gaseous oxides of nitrogen and are usually abbreviated to NO x because of the many oxidation states of the nitrogen There are several nitrogen-oxygen compounds.
  • the term "saturation / partial saturation of the exhaust gases with water” means that exhaust gases are saturated / partially saturated with, for example, a quencher / scrubber with water, and the exhaust gases are therefore preferred up to their dew point with water vapor
  • the exhaust gases should have at least a relative humidity of 50%, preferably 60%, particularly preferably 80%.
  • the exhaust gases are passed before step b) in a pre-reactor, which contains a second catalyst and then in step b) saturated with water or partially saturated.
  • the exhaust gases are passed to step b) in a pre-reactor, which contains a second catalyst and then introduced into the reactor in step c).
  • the second catalyst in the pre-reactor is preferably used in a dry state, i. E. no water is given off and care is taken to ensure that no condensation forms during the reaction.
  • care must be taken that the dew point of the gases is not undershot during their residence time in the pre-reactor.
  • washing out of the catalyst with water is understood in the context of the present invention, the imparting of water in the upper part of the reactor, wherein the water then in countercurrent to the gases flows through the reactor.
  • the water can also be added in cocurrent to the gases.
  • the carbon after the reaction is discharged as a solid by washing the catalyst from the reactor. It can exist as both C and C compounds.
  • C compounds in the context of the present invention is understood as meaning C (NO) complexes and other compounds between C, N and O.
  • carbon is understood in the context of the present invention to mean both carbon (C ) as well as C compounds such as C (NO) complexes and other compounds between C, N and O.
  • exhaust gases are treated which contain between 100 and 1500 ppm of NOx and between 0.3 and 15 vol.% CO2.
  • CO 2 and NO x are removed from the exhaust gases at the same time to the extent contained in the exhaust gases CxHy - but [0022] According to a preferred embodiment of the invention may also CxHy - as additional pollutants.
  • C x H y is understood in the context of the present invention compounds which consist only of carbon and hydrogen, such as straight-chain or branched alkanes, cycloalkanes, straight-chain or branched alkenes, straight-chain or branched alkynes and aromatics ,
  • the content of CxHy of the gases to be treated is preferably between 0 and 700 ppm C x H y .
  • the inlet temperatures of the exhaust gases in the reactor are preferably between the ambient temperature and 150 ° C. Higher temperatures could permanently damage the catalyst.
  • the oxygen content of the exhaust gases is actually not critical, but it should ideally be at least 5% by volume, preferably at least 8% by volume, more preferably at least 10% by volume, and in particular at least 12% by volume.
  • the saturation of the exhaust gases with water can be easily carried out by quenching or with a scrubber or a similar method.
  • the exhaust gases should contain as little as possible solids, dust and the like to prevent poisoning and / or clogging of the catalyst.
  • This dedusting of the exhaust gases is achieved by conventional filtration systems before the exhaust gases are then passed into the quencher or the scrubber.
  • the cleaning factor of CO2 is influenced by the washing out of the activated carbon bed.
  • a base e.g. 5-30% NaOH solution can achieve a CO2 capture of over 90%.
  • base is understood in the context of the present invention, an aqueous solution of M n + (OH " ) n wherein M is selected from the groups consisting of alkali metals and alkaline earth metals and wherein n is 1, 2 or 3.
  • M is selected from the groups consisting of alkali metals and alkaline earth metals and wherein n is 1, 2 or 3.
  • an aqueous NaOH solution is used.
  • the concentration of the base is ideally in the order of 5 - 30% by weight in water.
  • the introduction of very fine water droplets with or without M n + (OH " ) n in the flue gas result in a lowering of the temperature and, inter alia, an increase of the water content with optionally a corresponding M n + (OH " ) n content up to a relative humidity of max. 100% in the flue gas.
  • the washing out of the activated charcoal bed can also be positively influenced by mixing cationic, anionic, nonionic or amphoteric surfactants in the water or base used to wash off the catalyst.
  • surfactants is understood in the context of the present invention, substances which reduce the surface tension of a liquid or the interfacial tension between two phases and allow or support the formation of dispersions or act as a solubilizer.
  • FIG. 2 is a graphical representation of the CO 2 , NO x and O 2 contents of the exhaust gases at the inlet and outlet of the reactor measured in the first experimental order, the catalyst being washed out with NaOH, FIG.
  • FIG. 4 is a graph of the CO 2 , NO x and O 2 contents of the exhaust gases at the inlet and outlet of the reactor measured in the first experimental order, wherein the catalyst was washed out with water, FIG.
  • Fig. 5 is a graph of measured in the first experimental order values of CO 2 , NO x , C x H y and O 2 content of the exhaust gases at the inlet or outlet of the reactor, wherein the catalyst was washed out with water .
  • Figure 5a is a graphic representation of the mean values measured in the first experimental set-up of several experiments of CO 2 and NO x removal of the exhaust gases at the inlet or outlet of the reactor, wherein the catalyst was washed out with NaOH.
  • 6 is a schematic representation of the second experimental arrangement
  • 7 is a graphical representation of the measured in the second experimental order values of CO 2 , NO x and O 2 content of the exhaust gases at the inlet of the pre-reactor or outlet of the reactor, wherein the catalyst was leached in the second reactor with NaOH,
  • Fig. 8 is a graph of measured in the second experimental order values of CO 2 , NO x , C x H y and O 2 content of the exhaust gases at the inlet of the pre-reactor or outlet of the reactor with the catalyst in the second reactor NaOH was washed out,
  • Fig. 9 is a graphical representation of measured in the second experimental order values of CO 2 , NO x and O 2 and C x H y content of the exhaust gases at the inlet of the pre-reactor or outlet of the reactor wherein the catalyst in the second reactor water was washed out,
  • Fig. 10 is a graph of measured in the second experimental order values of CO 2 , NO x , C x H y and O 2 content of the exhaust gases at the inlet of the pre-reactor or outlet of the reactor with the catalyst in the second reactor Water was washed out.
  • FIG. 11 is a graphic representation of the values of the CO 2 and NO x contents of the exhaust gases measured at the inlet or outlet of the prereactor, measured in the second experimental order.
  • the experimental arrangement 1 shown in Figure 1, for illustrating the invention, comprises a test reactor 1 10, in whose lower part 1 12, a test gas is supplied and in whose upper part 1 14 water or a base is sprayed.
  • the experimental exhaust comes from a combustion of natural gas (natural gas).
  • the exhaust gas is dedusted by means of an electrostatic precipitator (not shown) and passes through a blower 1 16 at about 300 ° C in a Venturi quenches 1 18.
  • the integrated in the mist eliminator 120 feed tank 122 of Venturi quencher 1 18 with water or a 15% NaOH solution.
  • the Exhaust gases are cooled down to saturation temperature in the Venturi quench 1 18 and saturated.
  • a first measuring device 124 analyzes the composition (NOx content, CO2 content, as well as O2 content and in some experiments CxHy content), the temperature, the flow rate and the flow rate of the test exhaust gas.
  • test gas then passes into the reactor 1 10th
  • the reactor 1 10 was filled with an activated carbon catalyst 130.
  • the test gas flows through the reactor 110 and the catalyst 130 located therein from the bottom to the top and, after exiting the reactor 1 10 in a second meter 132 to the same parameters as in the first meter 124 ie composition (NO x Content, CO2 content, as well as O2 content and in some experiments C x H y content), the temperature, the flow rate and the flow rate, tested and then discharged into the atmosphere through a chimney 134.
  • the NO x , CO2 and optionally C x H y is catalytically converted with continuous addition of a base or water (washing the activated carbon bed).
  • the water or base required in the reactor 110 is passed from a reservoir 136 by means of a pump 138 via a measuring device 140, where the flow is measured, into the upper part 114 of the reactor 110, where the water / base the activated carbon catalyst 130 flows through in countercurrent to the test gas.
  • the water required for the quench 1 18 comes directly from the water supply 142 and is circulated.
  • the base from the reservoir 144 is conveyed by means of a pump 146 into the reservoir 122 of the droplet 120 of the quench 1 18.
  • the water or base contained in the reservoir 122 of the mist eliminator 120 is conveyed by a pump 148 to the spray head 150 of the quench 18.
  • the reactor 110 has a filling body 152, which is located below the activated carbon catalyst 130. This packing 152 serves to distribute the gas and should consist of an inert material such as Al2O3. This packing ensures that the gases are distributed over the entire catalyst
  • the NO 3 " and carbon or carbon compounds formed by the reactions on the catalyst 130 are removed from the catalyst 130 by spraying with water or a base, depending on the volume of the activated carbon catalyst 130 and the NO x and CO 2 concentrations and additionally, if present , C x H y concentrations, rinsed in countercurrent to the gas.
  • the activated carbon catalyst 130 was continuously purged with a water / base amount of 5-20 l / min.
  • the amount of water / base needed depends on the pollutant concentrations. If not washed off sufficiently, according to the occurring pollutant concentrations, the pores of the activated carbon catalyst 130 can clog and the entire reactions come to a standstill.
  • the process water optionally together with the base and the resulting in the process and suspended therein carbon respectively.
  • Carbon compounds are collected in a container 154 and the pH is determined by a meter 156. Subsequently, the liquid is pumped off by a pump 158 and the flow rate is detected by a further measuring device 160.
  • the NO x of the exhaust gases is catalytically converted to NO 3 " on moist activated carbon catalyst granules, and simultaneously carbon dioxide is split into carbon and oxygen, or, if present, C xH y is converted to carbon and H 2 but also present as carbon compounds.
  • Tested activated carbon catalysts were tested by NORIT Nederland B.V. from Postbus 105 NL-3800 AC Amersfoort under the designations Norit_PK1-3, Norit_PK_2-4 and Norit_PK_3-5.
  • These activated carbon catalysts are an activated carbon granules, with a grain size between 1 -3 mm; 2-4 mm or 3-5 mm produced by steam activation.
  • the following general characteristics are guaranteed by the manufacturer: iodine number 800; Methylene blue adsorption 1 g / 100 g; Inner surface area (BET) 875 m 2 / g; Bulk density 260 kg / m 3 ; Density after backwashing 230 kg / m 3 ; Uniformity grade 1, 3 - ash content 7% by weight; pH alkaline; Moisture (packaged) 2% by weight.
  • the course of CxHy conversion to C and H2 on the catalyst surface can also be temporarily attached to the activated carbon and / or C compounds and / or other compounds here.
  • NOx and O2 migrate to the active centers of the catalyst.
  • NOx is here partially oxidized to NO2 and N2O3 and N 2 O 4 .
  • NO2 then travels from the active centers of the catalyst out and reacts with NaOH if available on the aqueous enclosure around the catalyst particle to NO2 ", NO3", and H 2 O.
  • the CO2 molecule also transported into the pores of the catalyst grain and separated there by supplying the formation energies, resp. is adsorbed on C compounds.
  • the NaOH solution if present, which is in the aqueous shell around the grain, adsorbed by high surface tensions (specific surface area) the C content of CO2 and O2. Also arise so-called carbon compounds.
  • softened water was used with or without the addition of base (e.g., NaOH).
  • base e.g., NaOH
  • the reactor in the experiments carried out is made of glass fiber reinforced plastic, has a volume of about 2 m 3 and is filled with 2 m 3 of an activated carbon catalyst of the type Norit_PK_2-4.
  • the pilot plant was driven at a throughput of about 220 m 3 / h with the addition of NOx between 500 and 800 ppm. Overall, the reactor was charged with about 8 kg of NOx (about 4 kg of NOx m 3 activated carbon catalyst) (FIG. 2).
  • the exhaust gases were cooled from about 300 ° C to about 60 ° C according to this test in a quench filled with a 15% NaOH base solution. In this case, the exhaust gas was saturated, that is, the exhaust gas had a relative humidity of about 100%.
  • the continuous wash water application which consisted of a 5-30% NaOH solution, was applied to the activated carbon catalyst at up to 10 l / min.
  • the NO x and the CO 2 content of the exhaust gases were in FIG. 1 in each case measured at the inlet and at the outlet of the reactor. The measurements were made every 60 seconds and plotted on Figures 2 and 3. The measurements shown in Figure 2 were made after saturation of the catalyst with NOx.
  • the CO2 concentration was between 4.8% and 5.6% by volume.
  • the purification of CO2 succeeded in the purification values of CO2 then continuously increased to 99.5%, unaffected by the increase or decrease in CO2 levels in the exhaust gas.
  • the test trial ran continuously over about 60 minutes. Over this entire period, the treated exhaust gases showed a reduction of NOx by about 30- 40%, as shown in FIG. 2 can be seen.
  • CxH y was also contained in the exhaust gas and was deposited to 100%.
  • the neutralization salts as well as the carbon / carbon compounds sedimented after a short time.
  • the second experimental arrangement shown in Figure 6, for illustrating the invention differs from the first experimental arrangement in that the experimental gas from the Quench 1 18 first in a pre-reactor 126 which is filled with a catalyst 128 and then in the reactor 1 10 is conducted.
  • This catalyst 128 of the pre-reactor 126 is an activated carbon catalyst from NORIT Nederland BV from Postbus 105 NL-3800 AC Amersfoort, which is provided under the names Norit_RST-3. It is an extruded activated carbon granulate with a grain size of 3 mm.
  • a pre-reactor 126 is used in the second experimental setup.
  • This prereactor 126 is acted upon without the addition of water or base with the exhaust gases from the quench 1 18.
  • the catalyst 128 in the prereactor 126 thus operates in principle “dry” while the catalyst in the reactor 110 operates “wet”: the catalyst 128 in the prereactor 126 remains “dry", since the temperature of the exhaust gases in this prereactor changes only insignificantly also no or only an insignificant condensation of the water vapor contained in the exhaust gases.
  • reaction which takes place on a "wet" catalyst is different from that on the catalyst of CN 101 564 640 because the catalyst is used under different conditions.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Biomedical Technology (AREA)
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  • Physics & Mathematics (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé pour l'élimination catalytique de dioxyde de carbone et de NOx d'effluents gazeux dans un réacteur rempli d'un catalyseur à charbon actif. Le procédé comprend les étapes suivantes : a. saturation du catalyseur par de l'eau; b. saturation ou saturation partielle des effluents gazeux par de l'eau; c. introduction des effluents gazeux dans le réacteur; d. conversion catalytique de NOx et NO2 - et parallèlement conversion catalytique sur le même catalyseur de CO2 en carbone O2; et e. lavage du catalyseur à charbon actif avec de l'eau et évacuation du carbone sous forme solide ainsi que de NO2 - dissous dans l'eau ou dans la base.
PCT/EP2012/072286 2011-11-14 2012-11-09 Procédé pour l'élimination catalytique de dioxyde de carbone et de nox de d'effluents gazeux WO2013072257A1 (fr)

Priority Applications (19)

Application Number Priority Date Filing Date Title
MX2014005774A MX349586B (es) 2011-11-14 2012-11-09 Procedimiento para la remocion catalitica de dioxido de carbono, nox, de los gases residuales.
CN201280055983.8A CN104254385B (zh) 2011-11-14 2012-11-09 用于将二氧化碳及氮氧化物从废气作催化去除的方法
KR1020147015844A KR20140101775A (ko) 2011-11-14 2012-11-09 배기가스로부터 이산화탄소 및 NOx의 촉매적 제거방법
SG11201401771TA SG11201401771TA (en) 2011-11-14 2012-11-09 PROCESS FOR THE CATALYTIC REMOVAL OF CARBON DIOXIDE, NO<sb>X</sb> FROM EXHAUST GASES
EP12781361.6A EP2782662B1 (fr) 2011-11-14 2012-11-09 Procédé pour l'élimination catalytique de dioxyde de carbone et de nox d'effluents gazeux
NO12781361A NO2782662T3 (fr) 2011-11-14 2012-11-09
BR112014011549A BR112014011549A2 (pt) 2011-11-14 2012-11-09 método para remoção catalítica de dióxido de carbono e nox de gases residuais em um reator carregado com catalisador de carvão ativado
JP2014540482A JP6614774B2 (ja) 2011-11-14 2012-11-09 触媒を用いた廃ガスからのＣＯ２及びＮＯｘ除去方法
DK12781361.6T DK2782662T3 (en) 2011-11-14 2012-11-09 METHOD OF CATALYTIC REMOVAL OF CARBON Dioxide AND NOX FROM COMBUSTION GAS
ES12781361.6T ES2666493T3 (es) 2011-11-14 2012-11-09 Procedimiento para la remoción catalítica de dióxido de carbono y NOx de gases de combustión
CA2852817A CA2852817C (fr) 2011-11-14 2012-11-09 Procede pour l'elimination catalytique de dioxyde de carbone et de nox de d'effluents gazeux
PL12781361T PL2782662T3 (pl) 2011-11-14 2012-11-09 Sposób katalitycznego usuwania dwutlenku węgla i NOx z gazów odlotowych
EA201400580A EA024177B1 (ru) 2011-11-14 2012-11-09 Способ каталитического удаления диоксида углерода и noиз отходящих газов
AU2012339000A AU2012339000B2 (en) 2011-11-14 2012-11-09 Process for the catalytic removal of carbon dioxide, NOx from exhaust gases
US14/357,498 US9375681B2 (en) 2011-11-14 2012-11-09 Process for the catalytic removal of carbon dioxide, NOx from exhaust gases
TNP2014000178A TN2014000178A1 (en) 2011-11-14 2014-04-25 PROCESS FOR THE CATALYTIC REMOVAL OF CARBON DIOXIDE, NOx FROM EXHAUST GASES
MA37089A MA35821B1 (fr) 2011-11-14 2014-05-29 Procédé pour l'élimination catalytique de dioxyde de carbone et de nox de d'effluents gazeux
ZA2014/04132A ZA201404132B (en) 2011-11-14 2014-06-05 Process for the catalytic removal of carbon dioxide,nox from exhaust gases
IN4592DEN2014 IN2014DN04592A (fr) 2011-11-14 2014-06-06

Applications Claiming Priority (2)

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LU91900 2011-11-14
LU91900A LU91900B1 (de) 2011-11-14 2011-11-14 Verfahren zur katalytischen Entfernung von Kohlendioxyd NOx aus Abgasen

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LU93012B1 (en) 2016-04-04 2017-11-08 Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A Sulfur dioxide removal from waste gas
LU93013B1 (en) 2016-04-04 2017-11-08 Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A Process for the removal of heavy metals from fluids
LU93014B1 (en) * 2016-04-04 2017-10-05 Ajo Ind S A R L Catalyst mixture for the treatment of waste gas
DE102018209993A1 (de) 2018-06-20 2019-12-24 ECOVAC Filteranlagen GmbH Vorrichtung und Verfahren zur Reinigung schadstoffbelasteter Luft
CN108975332B (zh) * 2018-07-19 2020-07-24 深圳市环球绿地新材料有限公司 高硬度活性炭、其制备方法和用途
DE102019207502A1 (de) 2019-05-22 2020-11-26 Christoph Kronhagel Luftreinigungsanlage
KR102465990B1 (ko) * 2021-12-30 2022-11-10 한국생산기술연구원 알카리 토금속계 건식 흡수제를 이용한 수분과 이산화탄소 동시 제거용 저온형 선택적 환원 촉매 복합시스템

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US20140314647A1 (en) 2014-10-23
CN104254385B (zh) 2017-05-31
SG11201401771TA (en) 2014-08-28
ZA201404132B (en) 2015-09-30
JP2018130720A (ja) 2018-08-23
EA201400580A1 (ru) 2014-11-28
PL2782662T3 (pl) 2018-07-31
NO2782662T3 (fr) 2018-07-07
MA35821B1 (fr) 2014-12-01
LU91900B1 (de) 2013-05-15
AU2012339000A1 (en) 2014-06-19
AU2012339000B2 (en) 2016-09-15
CA2852817A1 (fr) 2013-05-23
EP2782662B1 (fr) 2018-02-07
EA024177B1 (ru) 2016-08-31
KR20140101775A (ko) 2014-08-20
CA2852817C (fr) 2020-03-31
MX349586B (es) 2017-08-03
EP2782662A1 (fr) 2014-10-01
MX2014005774A (es) 2014-05-30
TW201336578A (zh) 2013-09-16
US9375681B2 (en) 2016-06-28
IN2014DN04592A (fr) 2015-05-08
UY34450A (es) 2013-05-31
JP2015501715A (ja) 2015-01-19
DK2782662T3 (en) 2018-04-16
CL2014001249A1 (es) 2014-10-03
TWI580467B (zh) 2017-05-01
AR088853A1 (es) 2014-07-10
BR112014011549A2 (pt) 2017-05-09
CN104254385A (zh) 2014-12-31
ES2666493T3 (es) 2018-05-04
TN2014000178A1 (en) 2015-09-30

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